CN115000503B - Mixed conductive slurry and method for improving stability thereof - Google Patents

Mixed conductive slurry and method for improving stability thereof Download PDF

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CN115000503B
CN115000503B CN202210915982.1A CN202210915982A CN115000503B CN 115000503 B CN115000503 B CN 115000503B CN 202210915982 A CN202210915982 A CN 202210915982A CN 115000503 B CN115000503 B CN 115000503B
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CN115000503A (en
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黄建
李立飞
金诚
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Jiangsu Langu New Energy Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the technical field of conductive paste, and discloses a mixed conductive paste and a method for improving the stability of the mixed conductive paste. The invention complexes with the electron-withdrawing effect formed by the solid electrolyte containing excessive lithium ions and the-CN with unsaturated group at one end of the functional additive to form a complex, and the hydroxyl and carboxyl on the surface of the conductive carbon material and the-OH, -COOH, -NH-or-NH at one end of the functional additive 2 The groups form non-covalent bond hydrogen bonds with strong polarity, so that the functional additive is simultaneously connected with the solid electrolyte and the conductive carbon material, the uniformly dispersed and stably dispersed mixed conductive slurry is obtained while floating and sinking of the conductive carbon material and the solid electrolyte are balanced, the obtained mixed conductive slurry has good ionic conductivity and electronic conductivity, the requirements on stability in the transportation, storage and use processes are met while the uniform dispersion is stable, and the storage time is effectively prolonged.

Description

Mixed conductive slurry and method for improving stability thereof
Technical Field
The application relates to the technical field of conductive paste, in particular to a mixed conductive paste and a method for improving the stability of the mixed conductive paste.
Background
The solid electrolyte is a fast ion conductor, and has good lithium ion conductivity and low electron conductivity. When the solid electrolyte is applied to a battery, a conductive carbon material needs to be added to improve the electronic conductivity. However, the conductive carbon material has a small specific gravity and is easily floated in water or an organic solvent.
The solid electrolyte powder is easy to agglomerate and not easy to be made into nano-scale, and the nano-scale slurry can be made by dispersing the powder in a solvent. The slurry can be classified into an aqueous slurry and an organic slurry. Because the solid electrolyte is heavy, the particle sedimentation phenomenon can occur in the slurry, so that the transportation, storage and use of the solid electrolyte slurry are seriously influenced due to the non-uniformity of the slurry.
Aiming at the physical stability of solid electrolyte slurry particle sedimentation, a dispersing agent is generally added into the slurry to improve the surface activity of particles, and a monomer formed by dissolving the dispersing agent is adsorbed on the surface of solute particles to form a steric hindrance stabilizing layer, so that the contact among the particles is hindered, and the particles are prevented from being coagulated to improve the physical stability. In the prior art, because of the large specific gravity of solid particles, the dispersant can alleviate the settling time of particles to a certain extent, but the settling still occurs in the solid electrolyte slurry when the storage time is long, and the improvement is needed.
Disclosure of Invention
In view of the above, a first object of the present application is to provide a mixed conductive paste for avoiding particle sedimentation. The specific scheme is as follows:
a mixed conductive paste comprising 1-80wt% of a solid electrolyte, 1-90wt% of a conductive carbon material, 0.1-10wt% of a functional additive, and a solvent as the balance; the functional additive is at least one of I, II, III and IV; wherein: i is
Figure 343085DEST_PATH_IMAGE001
(ii) a II is
Figure 464012DEST_PATH_IMAGE002
(ii) a III is a
Figure 405292DEST_PATH_IMAGE003
(ii) a IV is
Figure 79987DEST_PATH_IMAGE004
(ii) a And R1 and R2 are independently one of alkyl, alkoxy, aryl or heteroaryl.
Preferably: the hydrocarbyl group is C a H 2a+1 - 、C b H 2b-1 - Or C c H 2c-3 - (ii) a Wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6.
Preferably: said hydrocarbyloxy group is C a H 2a+1 O-、C b H 2b-1 O-or C c H 2c-3 O-; wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6.
Preferably: the aryl group is phenyl, anthryl, naphthyl or biphenyl.
Preferably: the carbon atom number of the heteroaryl is 3 to 20, and 1-3 atoms in O, S, P and N are included.
Preferably: the heteroaryl group is one of pyridyl, indolyl, pyrrolyl, imidazolyl, thienyl, furyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indole, isoindole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, benzoxazole, naphthoxazole, phenanthroizole, benzothiadiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, benzopyrazinyl, benzothiophenyl, benzopyrazolyl, carbazolyl, naphthothiadiazolyl.
Preferably: the solid electrolyte is NASICON type oxide solid electrolyte Li 1+x A x B 2-x (PO 4 ) 3 (ii) a Wherein A is at least one of Al, la, in, cr, ga, fe, sc, lu and Y; b is at least one of Ti, ge, zr, hf and Sn; x is more than or equal to 0 and less than or equal to 0.5.
Preferably: the solid electrolyte is a Garnet type oxide solid electrolyte Li x A 3 B 2 O 12 (ii) a Wherein A is at least one of La, nb, mg, ba, ca and Sr; b is at least one of Te, ta, nb, zr and In; x is more than 0 and less than or equal to 7.
Preferably: the solid electrolyte is Perovskite type oxide solid electrolyte Li 3x La 2/3-x TiO 3 ；0＜x≤2/3。
Preferably: the solid electrolyte is Anti-perovskite type oxide solid electrolyte Li 3 OX、Li 3- 2x A x BO、Li 1.9 OHCl 0.9 And Li 2 At least one of OHCI; wherein X is Cl and/or Br; a is Mg 2+ 、Ca 2+ 、Sr 2+ And Ba 2+ At least one of; b is Cl and/or I; x is more than or equal to 0 and less than 3/2.
Preferably: the solid electrolyte is Thio-LISICON type sulfide solid electrolyte (100-x) Li 2 S -x P 2 S 5 Or Li 4-y A 1-y B y S 4 Or Li 4 SnS 4 (ii) a Wherein x is more than 0 and less than 100; a is Ge and/or Si; b is at least one of P, al and Zn；0＜y＜1。
Preferably: the solid electrolyte is Li 11-x M 2-x P 1+x S 12 Type sulfide solid electrolytes; wherein M is at least one of Ge, sn and Si; x is more than or equal to 0 and less than or equal to 1.
Preferably: the Li 11-x M 2-x P 1+x S 12 The sulfide-type solid electrolyte is Li 10 GeP 2 S 12 、Li 10 SnP 2 S 12 Or Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 。
Preferably: the solid electrolyte is a silver germanite sulfide solid electrolyte Li 6 PS 5 X; wherein X is at least one of Cl, br and I.
Preferably: the solid electrolyte is a halide solid electrolyte A 3 MX 6 (ii) a Wherein A is Li and/or Na; m is at least one of trivalent metals In, Y, er, sc and Zr; x is at least one of Cl, br and I.
Preferably: the conductive carbon material is at least one of conductive carbon black Super-P, ketjen black ECP with a branched chain structure, conductive graphite KS-6, SFG-6, vapor grown carbon fiber VGCF, carbon nanotube CNTs, artificial graphite, natural graphite, hard carbon, soft carbon, graphene and graphene composite conductive agent.
Preferably: the solvent is water or a non-aqueous solvent; and the non-aqueous solvent comprises N-methylpyrrolidone, methanol, ethanol, acetone, acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, C n H 2n+2 、C n H 2n At least one of petroleum ether, cyclohexane, carbon tetrachloride, trichloroethylene, carbon disulfide, toluene, benzene, dichloromethane, chloroform, diethyl ether, ethyl acetate and acetone; wherein n is more than or equal to 5 and less than or equal to 12.
A second object of the present application is to provide a method for improving the stability of the mixed conductive paste as described above, comprising mixing a solid electrolyte, a solvent, a conductive carbon material and a functional additive; and one end of the functional additive isa-CN group, the other end being-OH, -COOH, -NH-or-NH 2 A group.
According to the scheme, the application provides the mixed conductive paste and the method for improving the stability of the mixed conductive paste, and the mixed conductive paste and the method for improving the stability of the mixed conductive paste form polar active reaction groups such as ketone groups, carboxyl groups and/or hydroxyl groups on the surface of a conductive carbon material of which the surface chemical components comprise C, N, O, H and other elements and trace metal impurities, and then are combined with the conductive carbon material of which one end is-OH, -COOH, -NH-or-NH 2 The functional additive of the group and hydroxyl and carboxyl on the surface of the conductive carbon material form a noncovalent bond hydrogen bond with stronger polarity; and the solid electrolyte containing excessive lithium ions and-CN with unsaturated groups at one end of the functional additive are complexed by an electron-withdrawing effect to form a complex, so that the functional additive is simultaneously connected with the solid electrolyte and the conductive carbon material, the uniformly dispersed and stably dispersed mixed conductive slurry is obtained while floating and sinking of the conductive carbon material and the solid electrolyte are balanced, the obtained mixed conductive slurry has good ionic conductivity and electronic conductivity, the requirements on stability in the transportation, storage and use processes are met while the uniform and stable dispersion is realized, and the storage time is effectively prolonged.
Detailed Description
The technical solutions in the embodiments of the present application will be described clearly and completely below, and it is obvious that the described embodiments are only some embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The following description will be made specifically for a mixed conductive paste and a method for improving the stability thereof according to an embodiment of the present invention:
a mixed conductive paste includes 1-80wt% of a solid electrolyte, 1-90wt% of a conductive carbon material, 0.1-10wt% of a functional additive, and a solvent as the balance.
The mixed conductive paste provided by the invention comprises 1-80wt% of the solid electrolyte, preferably 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or any value between 1-80 wt%.
The mixed conductive paste provided by the invention also comprises 1-90wt% of conductive carbon material, preferably 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or any value between 1-90 wt%.
The mixed conductive paste provided by the invention also comprises 0.1-10wt% of functional additive, preferably 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 7wt%, 10wt%, or any value between 0.1-10 wt%.
The mixed conductive paste provided by the invention also comprises the balance of solvent.
Wherein: the functional additive is at least one of I, II, III and IV; and I is
Figure 134531DEST_PATH_IMAGE001
(ii) a II is
Figure 485747DEST_PATH_IMAGE002
(ii) a III is a
Figure 399476DEST_PATH_IMAGE003
(ii) a IV is
Figure 205758DEST_PATH_IMAGE004
。
Specifically, R1 and R2 are one of alkyl, alkoxy, aryl or heteroaryl.
The hydrocarbon group is C a H 2a+1 - 、C b H 2b-1 - Or C c H 2c-3 - (ii) a Wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6. Alkoxy being C a H 2a+1 O-、C b H 2b-1 O-or C c H 2c-3 O-; wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6. Aryl is phenyl, anthracyl, naphthyl or biphenyl. The carbon number of the heteroaryl is 3 to 20, and 1-3 atoms in O, S, P and N are included. And heteroaryl is pyridyl, indolyl, pyrrolyl, imidazolyl, thienyl, furyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridinyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indole, isoindole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, benzoxazole, naphthooxazole, phenanthrooxazole, benzothiadiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, benzopyrazinyl, benzothiophenyl, benzofuranyl, benzopyrryl, carbazolyl, naphthothiadiazolyl.
Preferably, the hydrocarbyl group is-CH 3 ；
The hydrocarbyloxy group is preferably an alkoxy group, more preferably-CH 2 -O-；
The aryl group is preferably phenyl;
the heteroaryl group is preferably pyridyl or thienyl.
Meanwhile, the solid electrolyte is NASICON type oxide solid electrolyte Li 1+x A x B 2-x (PO 4 ) 3 (ii) a Wherein A is at least one of Al, la, in, cr, ga, fe, sc, lu and Y; b is at least one of Ti, ge, zr, hf and Sn; x is more than or equal to 0 and less than or equal to 0.5. Preferably Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 。
Or as a Garnet-type oxide solid electrolyte Li x A 3 B 2 O 12 (ii) a Wherein A is at least one of La, nb, mg, ba, ca and Sr; b is at least one of Te, ta, nb, zr and In; x is more than 0 and less than or equal to 7. Preferably Li 7 La 3 Zr 2 O 12 。
Or as Perovskite type oxide solid electrolyte Li 3x La 2/3-x TiO 3 (ii) a X is more than 0 and less than or equal to 2/3. Preferably Li 0.30 La 0.567 TiO 3 。
Or Anti-perovskite type oxide solid electrolyte Li 3 OX、Li 3-2x A x BO、Li 1.9 OHCl 0.9 And Li 2 At least one of OHCI; wherein X is Cl and/or Br; a is Mg 2+ 、Ca 2+ 、Sr 2+ And Ba 2+ At least one of; b is Cl and/or I; x is more than or equal to 0 and less than 3/2. Preferably Li 3 OCl。
Or a Thio-LISICON type sulfide solid electrolyte (100-x) Li 2 S-xP 2 S 5 Or Li 4-y A 1-y B y S 4 Or Li 4 SnS 4 (ii) a Wherein x is more than 0 and less than 100; a is Ge and/or Si; b is at least one of P, al and Zn; y is more than 0 and less than 1. Preferably Li 7 P 3 S 11 。
Or is Li 11-x M 2-x P 1+x S 12 Type sulfide solid electrolytes; wherein M is at least one of Ge, sn and Si; x is more than or equal to 0 and less than or equal to 1. Preferably Li 10 GeP 2 S 12 、Li 10 SnP 2 S 12 Or Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 。
Or a sulfide solid electrolyte Li of the Geranite type 6 PS 5 X; wherein X is at least one of Cl, br and I. Preferably Li 6 PS 5 Cl。
Or as a halide solid electrolyte A 3 MX 6 (ii) a Wherein A is Li and/or Na; m is at least one of trivalent metals In, Y, er, sc and Zr; x is at least one of Cl, br and I. Preferably Li 3 YCl 6 。
In addition, the conductive carbon material is at least one of conductive carbon black Super-P, ketjen black ECP with a branched chain structure, conductive graphite KS-6, SFG-6, vapor grown carbon fiber VGCF, carbon nano tube CNTs, artificial graphite, natural graphite, hard carbon, soft carbon, graphene and graphene composite conductive agent. Carbon Nanotubes (CNTs) and graphene are preferable.
The solvent is water or non-aqueous solvent; and the non-aqueous solvent comprises N-methylpyrrolidone, methanol, ethanol, acetone, acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, C n H 2n+2 、C n H 2n Petroleum ether, cyclohexane, carbon tetrachloride, trichloroethylene, carbon disulfide, toluene, benzene, dichloromethane and chloroformAt least one of diethyl ether, ethyl acetate and acetone; wherein n is more than or equal to 5 and less than or equal to 12. Water and N-methylpyrrolidone are preferred.
A method for improving the stability of a mixed conductive paste as described above, comprising mixing a solid electrolyte, a solvent, a conductive carbon material, and a functional additive; one end of the functional additive is-CN group, and the other end is-OH, -COOH, -NH-or-NH 2 A group.
Example one
A mixed conductive paste comprises, by mass, 10:80:5:5, a solvent, a conductive carbon material and a functional additive.
Wherein the fixed electrolyte is Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 And the micron-sized product with the grain diameter of 3-10 mu m is obtained after jaw crushing, roller pair and airflow crushing.
Meanwhile, the solvent is water, the conductive carbon material is graphene, and the functional additive is
Figure 770600DEST_PATH_IMAGE005
。
When the mixed conductive slurry is mixed, components with corresponding mass ratios are guided into a circulation material tank of a sand mill to be subjected to circular sanding nano-crystallization, and the corresponding mixed conductive slurry is obtained when the particle size reaches 50-100 nm.
In this embodiment, the method for improving the stability of the mixed conductive paste as described above includes mixing Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Water, graphene and
Figure 777871DEST_PATH_IMAGE005
。
example two
The difference between the second embodiment and the first embodiment is that the fixed electrolyte in the second embodiment is Li 0.30 La 0.567 TiO 3 The conductive carbon material is conductive carbon black Super-P and the functional additive is
Figure 37951DEST_PATH_IMAGE006
。
When the mixed conductive slurry is mixed, components with corresponding mass ratios are guided into a circulation material tank of a sand mill to be subjected to circular sanding nano-crystallization, and the corresponding mixed conductive slurry is obtained when the particle size reaches 100-200 nm.
EXAMPLE III
The difference between the third embodiment and the first embodiment is that the mixed conductive paste in the third embodiment comprises, by mass, 10:75:5:10, a solvent, a conductive carbon material, and a functional additive.
Wherein the fixed electrolyte is Li 7 La 3 Zr 2 O 12 The solvent is N-methyl pyrrolidone, the conductive carbon material is Carbon Nano Tubes (CNTs), and the functional additive is
Figure 775487DEST_PATH_IMAGE007
。
When the mixed conductive slurry is mixed, components with corresponding mass ratios are guided into a sand mill circulation material tank to be subjected to circular sanding nanocrystallization, and corresponding mixed conductive slurry is obtained when the particle size reaches 200-300 nm.
Example four
The difference between the fourth embodiment and the first embodiment is that the functional additive in the fourth embodiment is
Figure 70202DEST_PATH_IMAGE008
。
EXAMPLE five
The difference between the fifth embodiment and the second embodiment is that the functional additive in the fifth embodiment is
Figure 248374DEST_PATH_IMAGE009
。
EXAMPLE six
The difference between the sixth embodiment and the third embodiment is that the functional additive in the sixth embodiment is
Figure 120384DEST_PATH_IMAGE010
。
EXAMPLE seven
The difference between the seventh embodiment and the first embodiment is that the functional additive in the seventh embodiment is
Figure 534048DEST_PATH_IMAGE011
。
Example eight
The difference between the eighth embodiment and the second embodiment is that the functional additive in the eighth embodiment is
Figure 558635DEST_PATH_IMAGE012
。
Example nine
The difference between the ninth embodiment and the third embodiment is that the functional additive in the ninth embodiment is
Figure 32342DEST_PATH_IMAGE013
。
Example ten
The difference between the tenth embodiment and the first embodiment is that the functional additive in the tenth embodiment is
Figure 391648DEST_PATH_IMAGE014
。
Comparative example 1
The difference between the first comparative example and the first example is that the mixed conductive paste in the first comparative example comprises the following components in a mass ratio of 10:80:10 solid electrolyte, solvent, conductive carbon material.
Comparative example No. two
The difference between the second comparative example and the second example is that the mixed conductive paste in the second comparative example comprises the following components in a mass ratio of 10:80:10 solid electrolyte, solvent, conductive carbon material.
Comparative example No. three
The difference between the third comparative example and the second example is that the mixed conductive paste in the third comparative example comprises the following components in percentage by mass: 80:10 solid electrolyte, solvent, conductive carbon material.
The results of the sedimentation, ionic conductivity and electronic conductivity measurements on the samples of examples one to ten and comparative examples one to three are shown in table one.
Table-settlement test result table
Figure 218790DEST_PATH_IMAGE015
According to the table one, under the condition of the mixed conductive paste obtained by supplementing different functional additives, when the method is adopted to add the corresponding functional additive into the mixed conductive paste product, compared with the mixed conductive paste without the functional additive, the product has better anti-settling property, so that the aim of avoiding particle settling is fulfilled.
In summary, the mixed conductive paste and the method for improving the stability thereof of the present application form polar active reaction groups such as ketone group, carboxyl group and/or hydroxyl group on the surface of the conductive carbon material with surface chemical components containing C, N, O, H and other elements and trace metal impurities, and further combine the conductive carbon material with one end of-OH, -COOH, -NH-or-NH 2 The functional additive of the group and hydroxyl and carboxyl on the surface of the conductive carbon material form a noncovalent bond hydrogen bond with stronger polarity; and the solid electrolyte containing excessive lithium ions and-CN with unsaturated groups at one end of the functional additive are complexed by an electron-withdrawing effect to form a complex, so that the functional additive is simultaneously connected with the solid electrolyte and the conductive carbon material, the uniformly dispersed and stably dispersed mixed conductive slurry is obtained while floating and sinking of the conductive carbon material and the solid electrolyte are balanced, the obtained mixed conductive slurry has good ionic conductivity and electronic conductivity, the requirements on stability in the transportation, storage and use processes are met while the uniform and stable dispersion is realized, and the storage time is effectively prolonged.
References in this application to "first," "second," "third," "fourth," etc., if any, are intended to distinguish between similar elements and not necessarily to describe a particular order or sequence. It should be understood that the data so used may be interchanged under appropriate circumstances such that the embodiments described herein may be practiced in sequences other than those described. Moreover, the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, or apparatus.
It should be noted that the descriptions in this application referring to "first", "second", etc. are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between the embodiments may be combined with each other, but must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope claimed in the present application.
The principle and the implementation of the present application are explained herein by applying specific examples, and the above description of the embodiments is only used to help understand the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (14)

1. A mixed conductive paste, characterized in that: comprises 1-80wt% of solid electrolyte, 1-90wt% of conductive carbon material, 0.1-10wt% of functional additive and solvent as the rest; the functional additive is at least one of I, II, III and IV; wherein: i is
Figure DEST_PATH_IMAGE002
(ii) a II is
Figure DEST_PATH_IMAGE004
(ii) a III is
Figure DEST_PATH_IMAGE006
(ii) a IV is
Figure DEST_PATH_IMAGE008
(ii) a And R1 and R2 are independently one of alkyl, alkoxy, aryl or heteroaryl;
the hydrocarbyl group is C a H 2a+1 - 、C b H 2b-1 - Or C c H 2c-3 - (ii) a Wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6;
said hydrocarbyloxy group is C a H 2a+1 O-、C b H 2b-1 O-or C c H 2c-3 O-; wherein a is more than 0 and less than or equal to 6,0 and more than or equal to b and less than or equal to 6,0 and more than or equal to c and less than or equal to 6;
the aryl is phenyl, anthryl, naphthyl or biphenyl;
the carbon atom number of the heteroaryl is 3 to 20, and 1-3 atoms in O, S, P and N are included.
2. The mixed conductive paste according to claim 1, wherein: the heteroaryl group is one of pyridyl, indolyl, pyrrolyl, imidazolyl, thienyl, furyl, 1,2-thiazolyl, 1,3-thiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, thiadiazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, pyridyl, pyrazinyl, pyrimidinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, indole, isoindole, benzimidazole, naphthoimidazole, phenanthroimidazole, benzotriazole, benzoxazole, naphthoxazole, phenanthroizole, benzothiadiazolyl, benzotriazolyl, quinolinyl, isoquinolinyl, benzopyrazinyl, benzothiophenyl, benzopyrazolyl, carbazolyl, naphthothiadiazolyl.
3. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is NASICON type oxide solid electrolyte Li 1+x A x B 2-x (PO 4 ) 3 (ii) a Wherein A is at least one of Al, la, in, cr, ga, fe, sc, lu and Y; b is at least one of Ti, ge, zr, hf and Sn; x is more than or equal to 0 and less than or equal to 0.5.
4. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is a Garnet type oxide solid electrolyte Li x A 3 B 2 O 12 (ii) a Wherein A is at least one of La, nb, mg, ba, ca and Sr; b is at least one of Te, ta, nb, zr and In; x is more than 0 and less than or equal to 7.
5. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is Perovskite type oxide solid electrolyte Li 3x La 2/3-x TiO 3 ；0＜x≤2/3。
6. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is Anti-perovskite type oxide solid electrolyte Li 3 OX、Li 3-2x A x BO、Li 1.9 OHCl 0.9 And Li 2 At least one of OHCI; wherein X is Cl and/or Br; a is Mg 2+ 、Ca 2+ 、Sr 2+ And Ba 2+ At least one of; b is Cl and/or I; x is more than or equal to 0 and less than 3/2.
7. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is Thio-LISICON type sulfide solid electrolyte (100-x) Li 2 S -x P 2 S 5 Or Li 4-y A 1-y B y S 4 Or Li 4 SnS 4 (ii) a Wherein x is more than 0 and less than 100; a is Ge and/or Si; b is at least one of P, al and Zn; y is more than 0 and less than 1.
8. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is Li 11-x M 2- x P 1+x S 12 Type sulfide solid electrolytes; wherein M is at least one of Ge, sn and Si; x is more than or equal to 0 and less than or equal to 1.
9. The mixed conductive paste according to claim 8, wherein: the Li 11-x M 2-x P 1+x S 12 The sulfide-type solid electrolyte is Li 10 GeP 2 S 12 、Li 10 SnP 2 S 12 Or Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 。
10. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is a silver germanite sulfide solid electrolyte Li 6 PS 5 X; wherein X is at least one of Cl, br and I.
11. The mixed conductive paste according to claim 1, wherein: the solid electrolyte is a halide solid electrolyte A 3 MX 6 (ii) a Wherein A is Li and/or Na; m is at least one of trivalent metals In, Y, er, sc and Zr; x is at least one of Cl, br and I.
12. The mixed conductive paste according to claim 1, wherein: the conductive carbon material is at least one of conductive carbon black Super-P, ketjen black ECP with a branched chain structure, conductive graphite KS-6, SFG-6, vapor grown carbon fiber VGCF, carbon nanotube CNTs, artificial graphite, natural graphite, hard carbon, soft carbon, graphene and graphene composite conductive agent.
13. The mixed conductive paste according to claim 1, wherein: the solvent is water or a non-aqueous solvent; and the non-aqueous solvent comprises N-methylpyrrolidone, methanol, ethanol, acetone, acetonitrile, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, C n H 2n+2 、C n H 2n At least one of petroleum ether, cyclohexane, carbon tetrachloride, trichloroethylene, carbon disulfide, toluene, benzene, dichloromethane, chloroform, diethyl ether, ethyl acetate and acetone; wherein n is more than or equal to 5 and less than or equal to 12.
14. A method for improving the stability of the mixed conducting paste according to any one of claims 1 to 13, characterized in that: comprising mixing a solid electrolyte, a solvent, a conductive carbon material, and a functional additive; one end of the functional additive is-CN group, and the other end is-OH, -COOH, -NH-or-NH 2 A group.
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